Phenyl-azo-pyrazolone dyes containing two sulfo groups

ABSTRACT

Dyestuffs of formula   IN WHICH R signifies a substituted or unsubstituted hydrocarbon radical, R1 signifies a substituted or unsubstituted phenylene or naphthylene radical, R2 signifies a substituted or unsubstituted alkyl or aryl radical, R3 signifies a hydrogen atom, a substituted or unsubstituted alkyl radical of one to six carbon atoms or a halogen atom, and RING A may be further substituted, USEFUL FOR DYEING AND PRINTING POLYAMIDE, CELLULOSIC AND BASIC DYEABLE POLYPROPYLENE FIBRES, LEATHER AND PAPER.

United States Patent 1191 Benz et al.

[ 51 Oct. 1,1974

1 1 PHENYL-AZO-PYRAZOLONE DYES CONTAINING TWO SULFO GROUPS [73] Assignee: Sandoz Ltd., Basel, Switzerland [22] Filed: Jan. 14, 1972 [21] Appl, No.: 217,946

[30] Foreign Application Priority Data Jan. 20, 1971 Switzerland 781/71 Jan. 22, 1971 Switzerland 986/71 [52] US. Cl 260/162, 8/41 R, 8/41 A, 8/41 D, 260/163, 260/470 [51] Int. Cl C091) 29/38 [58] Field 01 Search 260/162, 163

[56] References Cited UNITED STATES PATENTS 1,758,385 5/1930 Wagner et a1. 260/163 2,015,225 9/1935 Kracker et a1. 260/163 2,773,055 12/1956 Hindermann et a1 260/163 3,139,420 6/1964 Beffa et al. 260/149 3,222,354 12/1965 Lange 260/163 FOREIGN PATENTS OR APPLICATIONS 341,586 11/1959 Switzerland 260/163 644,153 10/1928 France 260/162 1,175,666 12/1969 Great Britain 260/163 Primary Examiner-Lorraine A. Weinberger Assistant Examiner-C. F. Warren Attorney, Agent, or Firm-Gerald D. Sharkin; Richard E. Vila; Melvyn M. Kassenoff [5 7] ABSTRACT Dyestuffs of formula SOsH Rs IIh-S 0 11 I in which R signifies a substituted or hydrocarbon radical, R signifies a substituted or unsubstituted phenylene or naphthylene radical, R signifies a substituted or unsubstituted alkyl or aryl radical, R signifies a hydrogen atom, a substituted, or unsubstituted alkyl radical of one to six carbon atoms or a halogen atom, and ring A may be further substituted, useful for dyeing and printing polyamide, cellulosic and basic dyeable polypropylene fibres, leather and paper.

unsubstituted 19 Claims, No Drawings PI-IENYL-AZO-PYRAZOLONE DYES CONTAINING TWO SULFO GROUPS The invention relates to azo dyes containing sulphonic acid groups.

According to the present invention, there are provided compounds of formula I,

1 A 2 N=N-oo-R, ILI

NH-COOR in which R signifies a substituted or unsubstituted hydrocarbon radical,

R signifies a substituted or unsubstituted phenylene or naphthylene radical,

R signifies a substituted or unsubstituted alkyl or aryl radical,

R signifies a hydrogen atom, a substituted or unsubstituted alkyl radical of l to 6 carbon atoms or a halogen atom, and

ring A may be further substituted.

Examples of hydrocarbon radicals include substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl or aryl radicals, e.g. cyclohexyl, alkylcyclohexyl, phenyl and naphthyl radicals.

As used herein, the term alkyl signifies a straight or branched chain alkyl radical of l to 18 carbon atoms, e.g. of 1 to 12 carbon atoms, particularly of l to 6 carbon atoms. Preferred alkyl radicals are from 1 to 4 carbon atoms except that, where R signifies an alkyl radical, such alkyl radical preferably contains 6 to 18 carbon atoms. The alkyl radicals may be substituted by, for example, halogen, hydroxy, cyano, alkoxy or aryl substituents. Suitable aryl substituted alkyl radicals include the benzyl radical. As used herein, the term alkoxy signifies an alkoxy radical containing from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms.

As used herein, the term cycloalkyl signifies a cyclcalkyl radical of to 7 carbon atoms.

Examples of aryl include phenyl and naphthyl radicals.

The aromatic rings, for example ring A and R may be substituted, for example, by one or more halogen, cyano, nitro, hydroxy, trifluoroalkyl, trichloroalkyl, substituted or unsubstituted alkyl, cycloalkyl, aryl, alkoxy, carbalkoxy, acylamino, substituted, e.g. mono or disubstituted, or unsubstituted sulphonamido, substituted or unsubstituted alkylsulphonyl, arylsulphonyl, carboxylic acid ester or sulphonic acid ester, substituted or unsubstituted carboxylic acid amide or sulphonic acid groups.

By halogen is meant bromine, fluorine, iodine or chlorine, chlorine being preferred.

It is preferred that the compounds of formula I contain no metallizable group in the ortho-position to the N=N-group in ring A.

The invention also provides a process for the production of a compound of formula I, stated above, characterised by (a) coupling a diazo derivative of an amine of formula II,

NH-COOR in which R, R and ring A are as defined above, with a compound of formula III,

fir-'5 0311 III in which R and R are as defined above, or (b) reacting a monoazo compound of formula IV,

SOaH

Ir-S 0311 IV in which R,, R R and ring A are as defined above, with a haloformic acid ester of formula V,

in which Hal signifies a fluorine, chlorine, bromine or iodine atom, and R is as defined above.

Process (a) may be carried out in conventional manner for diazo couplingreactions, for example in an acid medium, e.g. at a pH value of from 2 to 6.

Process (b) may, similarily, be carried out in conventional manner, for example in water and in the presence of an acid binding agent and at a temperature from 40 to 150C, especially 40 to 100C, and preferably from 60 to C.

Process (b) is the preferred process.

The resulting compounds of formula I may be isolated by conventional techniques.

The compounds of formula IV, used as starting materials in process (b), may be obtained by coupling a 2- diazo derivative of an amine of formula VI,

SOaH Ra M2 NH:

NH-B VI in which R and ring A are as defined above, and B signifies a hydrogen atom or an acetyl group with a compound of formula III, stated above, and, where B signifies an acetyl group, deacetylating the resulting product. The coupling reaction may be carried out in similar manner to process (a) described above. The deacetylation may be carried out in conventional manner.

The compounds of formulae II, III, IV, V and VI are known or may be obtained in known manner from available starting materials.

Particular compounds of formula I are the compounds of the following formulae Ia, lb and Ic.

N NH-COOR R3 SOaH in which R and ring A are as defined above, R signifies a substituted or unsubstituted alkyl, aryl or cycloalkyl radical, and R R and R,,, which may be the same or different,

each signifies a hydrogen or halogen atomor a substituted or unsubstituted alkyl or alkoxy radical,

in which R R and ring A are as defined above,

R signifies a hydrogen or halogen atom or an alkyl radical of l to 6 carbon atoms, and

R signifies a hydrogen or halogen atom, an alkyl radical of l to 6 carbon atoms or an alkoxy radical of l to 6 carbon atoms.

The compounds of formula I may suitably be used for dyeing and printing natural and synthetic polyamide fibres and other textile fibres. In particular, they may be used for exhaust dyeing, pad-dying and printing of natural and synthetic polyamide fibres, natural and regenerated cellulosic fibres and basic dyeable polypropylene fibres, which fibres may be dyed in loose, yarn,

fabric or blended form. The compounds of formula l may also suitably be used for dyeing and printing paper and leather.

In exhaust dyeing, the compounds are conveniently applied from a neutral to acid bath at a pH value of 2 to 7, preferably from 4 to 5, in the presence of an acid, e.g. an organic acid such as acetic or formic acid. The dyeings have good light and wet fastness, e.g. fastness to washing, sea water, perspiration, acid, alkali, aldehyde, potting and milling, and good fastness to gas fumes. They are also fast to rubbing. The dyes are well soluble in water, show satisfactory levelling properties and cover barry nylon.

The compounds of the present invention can be applied alone, in combination with each other or with acid dyes, e.g. of the anthraquinone series, to give dyeings of comparably good light and wet fastness. If the compounds of formula I are used in combination with blue dyes, eg blue anionic anthraquinone dyes, the dyeings are free from catalytic fading.

For printing with the present dyes known methods can be employed, for instance that described in U.S. Pat. No. 3,594,112.

Natural polyamide fibres which may be dyed with the dyes of the invention include wool and silk. Synthetic polyamide fibres which may be dyed include those from polymers formed by condensation polymerization of m-aminocarboxylic acids or their lactams, eg the fibres from w-lauric lactam ll-undecano-carboxylic acid, 7-aminoenanthic acid or e-caprolactam (polyamides 12, ll, 7 and 6), of dibasic organic acids, e.g. dicarboxylic acids 7 adipic, sebacis acid) and diamines (e.g. hexamethylene diamine) (polyamides 66 and 610), or by mixed condensation polymerization, e.g. of e-caprolactam, adipic acid and hexamethylene diamine (polyamide 66/6).

In comparison with the known dyes, eg those disclosed in Swiss Pat. No. 341,586, the compounds of formula I, have the advantage of being more suitable for application to natural and synthetic polyamide fibres by printing processes. In addition, they have noteworthy solubility in water.

The following Examples, in which the parts and percentages are by weight and the temperatures in degrees Centigrade, illustrate the invention.

EXAMPLE 1 i. Process (a) 20 parts of 2-amino-4- carbododecyloxyaminobenzenel -sulphonic acid (which is obtainable by reaction of 2,4-diaminobenzene-l-sulphonic acid with lauryl chloroformate) are stirred into 300 parts of water at room temperature and 6.7 parts of 30 percent aqueous sodium hydroxide solution are added, 3.5 parts of sodium nitrite are added and stirring is continued until a solution is obtained. Over 30 minutes, the solution is dropwise added, with stirring, to 30 parts of concentrated hydrochloric acid and 150 parts of water at 0-5. The resulting suspension is stirred for 1 hour at 05 and then added, dropwise, to a cooled solution consisting of 14.8 parts of l-( 2"chloro-5 -sulpho )-phenyl-3-methyl-5- pyrazolone, 6.7 parts of a 30 percent aqueous sodium hydroxide solution and parts of water, with care being taken to keep the temperature below 10. While the diazo suspension is being added, the pH of the coupling mixture is held at 5 by the gradual addition of 10 percent aqueous soda solution. The coupling mixture is stirred for a further 3 hours. The dye formed settles out and is isolated by filtration, with suction, and is then dried. It is obtained as a yellow powder which, applied from a neutral to weakly acid bath, dyes wool and synthetic polyamide fibres in yellow shades, fast to light, washing and milling.

ii. Process (b) 26.5 Parts of the disodium salt form of the monoazo dye obtained by coupling diazotized-2-amino-4- acetylamino-benzene-l-sulphonic acid with l-(2" chloro-5'-sulpho)-phenyl-3-methyl-5-pyrazolone are dissolved in 300 parts of water and 300 parts of alcohol. Then, 25 parts of concentrated hydrochloric acid are added. The temperature of the solution is raised to 85 and stirred at this temperature for 3 hours. After it has cooled to room temperature, the precipitated deacetylated product is filtered, washed until neutral, and dissolved in 800 parts of water containing 5 parts of soda. The solution is heated to 50 and held at this temperature for 3 hours while 25 parts of lauryl chloroformate are dropwise added thereto. Throughout the reaction, the pH is maintained at 7.5 8 by the addition of irfivhich R' la and R have the significances given in the table. The shade of the dyeings on synthetic polyamide fibre is noted in the final column.

Table Shade of Example dyeing on No. R" R, R synthetic polyamide fibre 2 Dodecyl (2-Chloro-6'- H yellow methyl-4'-sulji l-u il 3 do. (2,5'- ich oro- H do.

4'-sulpho)-phenyl 4 Decyl do. H do. 5 Undecyl do. H do. 6 Nonyl do. H do. 7 lso-octyl do. H do. 8 Di-isobutyl do. H do. 9 Heptyl do. H do. 10 Z-Ethyl-hexyl do. H do. 1 l Cyclohexyl do. H do. 12 p-Ethyl-cyclodo. H do.

hexyl l3 3',4',5'-Trido. H do.

methylcyclohexyl l4 p-Tert-butyldo. H do.

cyclohexyl l5 Benzyl do. H do. 16 Ethylphenyl do. H do. 17 Tridecyl do. H do. 13 n-Tetradecyl do. H do.

Table Contmued dShode of I yemg on Example synthetic o. polyamide fibre (2',5'-Dichloro- 4'-sulpho)- 19' iFPhTd'Ef I" phenyl H yellow 20 n-Hexadecyl do. H do. 21 n-Heptadecyl do. H do. 22 Decyl (2'-ChIoro-5'- H do.

sulpho)-phenyl 23 Undecyl do. H do. 24 Nonyl do. H do. 25 lso-octyl do. H do. 26 Di-isobutyl do. H do. 27 Heptyl do. H do. 28 Z-Ethyl-hexyl do. H do. 29 Cyclohexyl do. H do. 30 p-Ethyl-cyclodo. H do.

hexyl 31 3'.3,5'-Trido. H do.

methylcyclohexyl 32 p-Tert-butyldo. H do.

cyclohexyl 33 Benzyl do. H do. 34 Ethylphenyl do. H do. 35 Tridecyl do. H do. 36 n-Tetradecyl do. H do. 37 n-Pentadecyl do. H do. 38 n'Hexadecyl do. H do. 39 n-Heptadecyl do. H do. 40 Decyl (2'-Chloro-6'- H do.

methyl-4-sulpho)-phenyl 41 Undecyl do. H do. 42 Nonyl do. H do. 43 lso-octyl do. H do. 44 Di-isobutyl do. H do. 45 Heptyl do. H do. 46 Z-Ethyl-hexyl do. H do. 47 Cyclohexyl do. H do. 48 p-Ethyl-cyclodo. H do.

hexyl 49 3',3',5'-Trido. H do.

methylcyclohexyl 50 p-Tert-butyldo. H do.

cyclohexyl 51 Benzyl do. H do. 52 Ethylphenyl do. H do. 53 Tridecyl do. H do. 54 n-Telradecyl do. H do. 55 n-Pentadecyl do. H do. 56 n-Hexadecyl do. H do. 57 n-Heptadecyl do. H V d o 58 Dodecyl l'-Sulpho)-2'- H do naphthyl 59 Decyl do. H do. 60 Undecyl do. H do. 61 Nonyl do. H do. 62 lso-octyl do. H do. 63 Di-isobutyl do. H do. 64 Heptyl do. H do. 65 2-Ethyl-hexyl do. H do. 66 Cyclohexyl do. H do. 67 p-Ethyl-cyclodo. H do.

hexyl 68 3',3,5'-Trido. H do.

methylcyclohexyl 69 p-Tert-butyl do. H do.

cyclohexyl 70 Benzyl do. H do. 71 Eth lphenyl do. H do. 72 Tri ecyl do. H do. 73 n-Tetradecyl do. H do. 74 n-Pentadecyl do. H do. 75 n-Hexadecyl do. H do. 76 n-Hepladecyl do. H do. 77 Dodecyl (2,5'-Di-chloro- -CH, do.

4'-sulpho)-phenyl 78 Decyl do. do. do. 79 Undecyl do. do. do. 80 Nonyl do. do. do. 8 l Iso-octyl do. do. do.

Table Contmued Shade of E l dyeiltzlg on Xamp I, synt etic R polyamide (2 ,5 -Dichlorov H W 4-sulpho)- M 82 Di-isobulyl phenyl CH yellow 83 Heptyl do. do. do. 84 Z-Ethyl-Hexyl do. do. do. 85 Cyclohexyl do. do. do. 86 p-Elhyl-cyclodo. do. do.

methylcyclohexyl 88 p-Tert-butyldo. do. do.

cyclohexyl 89 Benzyl do. do. do. 90 Ethylphenyl do. do. do. 9] Tridecyl do. do. do. 92 n-Tetradecyl do. do. do. 93 n-Pentadecyl do. do. do. 94 n-Hexadecyl do. do. do. 95 n-Heptadecy] do. do. U do. 96 Dodecyl (2'-Chloro-5'- N d o. 716."

sulpho)phenyl 97 Decyl do. do. do. 98 Undecyl do. do. do. 99 Nonyl do. do. do.

100 Iso-octyl do. do. do.

I 01 Di-isobutyl do. do. do.

102 Heptyl do. do. do.

103 Z-Ethyl-hexyl do. do. do.

104 cyclohexyl do. do. do.

105 p-Ethyl-cyclodo. do. do.

hexyl 106 3', 3,5'-Trido. do. do.

methylcyclohexyl l 07 p-Tert-butyl do. do. do.

cyclohexyl I08 Benzyl do. do. do.

109 Ethylphenyl do. do. do.

1 l0 Tridecyl do. do. do.

1 l l n-Tetradecyl do. do. do.

1 l2 n-Pemadecyl do. do. do.

113 n-Hexadecyl do. do. do.

[14 n-Heptadecyl do. do. do.

1 l5 Dodecyl 2'-Chloro-6'- do. do. mcthyl-4'-sulpho)-phenyl 1 l6 Decyl do. do. d0.

1 17 Undecyl do. do. do.

1 18 Nonyl do. do. do.

1 l9 lso-octyl do. do. do.

Di-isobutyl do. do. do. 121 Heptyl do. do. do. 122 2-Ethyl-hexyl do. do. do. 123 Cyclohexyl do. do. do. 124 p-Ethyl-cyclodo. do. do.

exyl I25 3',3',3,5-Tri do. do. do.

methylcyclohexyl l 26 p-Tertbulyldo. do. do.

cyclohexyl I27 Benzyl do. do. do. 128 Ethylphenyl do. do. do. 129 Tridecyl do. do. do. 130 n-Tetradecyl do. do. do. 131 n-Pentadecyl do. do. do. 132 n-Hexadecyl do. do. do. 133 n-Heptadecyl do. do. do. 134 Dodecyl (l'-Sulpho)-2'- do. do.

naphxhyl 135 Decyl do. do. do. I36 Undecyl do. do. do. 137 Nonyl do. do. do. I 38 lso-octyl do. do. do. 139 Di-isobutyl do. do. do. I40 Heptyl do. do. do. I 4 l Z-Ethyl-hexyl do. do. do. 142 Cyclohexyl do. do. do. 143 p-Ethyl-cyclodo. do. do.

hexyl 144 3',3', 5-Trido. do. do.

methylcyclohexyl 145 p-Tert-butyldo. do. do.

cyclohexyl I46 Benzy! do. do. do.

147 Ethylphenyl V do. do. do.

Table Contmued Shade of dyeing on Example synthetic No. R R1 R1 polyamidc fibre W. M8 Tridecyl naphth yl yellow 149 n-Telradecyl do. do. do. 150 n-Pentadecyl do. do. do. 151 n-Hexadecyl do. do. do. 152 n-Heptadecyl dn do. N do. 153 Dodecyl 2',5'-Dic1| loxlo- -Cl 7 d9.

4-sulpho)-phenyl 154 Decyl do do. do. 155 Undecyl do. do. do. 156 Nonyl do. do. do. .15.]. .LSQLQQX! .19 do... 158 Di-isobutyl do. do. do. 159 Heptyl do. do. do. 160 Z-Ethyl-hexyl do. do. do. 161 Cyclohexyl do. do. do. 162 pEthyl-cyclodo. do. do.

hexyl 163 3',3,5'-Trido. do. do.

methylcyclohexyl 164 p-Tert-butyldo. do. do. cyclohexyl 1 165 Benzyl do. do. do. 166 Ethylphenyl do. do. do 167 Tridecyl do. do. do. 168 n-Tetradecyl do. do. do. 169 n-Pentadecyl do. do. do. 170 n-Hexadecyl do. do. do. 171 n-Heptadecyl do. do. do. 172 Dodecyl (2'Ch1oro-5'- do. do.

sulpho)-phenyl 173 Decyl do. do. do. 174 Undecyl do. do. do. 175 Nonyl do. do. do. 176 lso-octyl do. do. do. 177 Di-isobutyl do. do. do. 178 Heptyl do. do. do. 179 2-Ethyl-hexyl do. do. do. 180 Cyclohexyl do. do. do. 181 p-Ethyl-cyclodo. do. do.

hexyl 182 3',3',5-tr1- do. do. do.

methylcyclohexyl l 83 p'Tert-butyldo. do. do.

cyclohexyl 184 Benzyl do. do. do. 1 85 Ethylphenyl do. do. do. 186 Tridecyl do. do. do. 187 n-Tetradecyl do. do. do. 188 n-Pentadecyl do. do. do. 189 n-Hexadecy1 do. do. do. 190 n-Heptacecyl do. do. do. 191 Dodecyl (2'-Chloro-6'- do. do.

methyl-4'-sulpho)-pheny1 192 Decyl do. do. do. 193 Undecyl do. do. do. 194 Nonyl do. do. do. 195 lso-octyl do. do. do. 196 Di-isobutyl do. do. do. 197 Heptyl do. do. do. 198 2-Ethyl-hexy1 do. do. do. 199 Cyclohexyl do. do. do. 200 p-Ethyl-cyclodo. do. do.

hexyl 201 3',3,5-Trido. do. do.

methylcyclohexyl 202 -Tert-butyldo. do. do.

cyclohexyl 203 Benzyl do. do. do. 204 Ethylphenyl do. do. do. 205 Tridecyl do. do. do. 206 n-tetradecyl do. do. do. 207 n-Pentadecyl do. do. do. 208 n-Hexadecyl do. do. do. 209 n-Heptadecyl do. do. do. 210 Dodecyl (l'-Su1pho)-2'- do. do.

naphthyl 21 I Decyl do. do. do. 212 Undecyl do. do. do. 213 Nonyl do. do. do. 214 lso-octyl do. do. do. 215 Do-isobutyl do. do. do. 216 Heplyl do. do. do.

Table Continued Shade of Example dyeing on No. R" R," R nynthctic polyumidc fibre (I '-Sulpho)-2- 2 I 7 Z-Ethyl-hexyl naphthyl -C| yellow 218 Cyclohexyl do. do. do. 219 p-EthyI-cyclodo. do. do.

hexyl 220 3',3',5'-Trido. do. do.

melhylcyclohexyl 22 I p-Tert-butyldo. do. do.

cyclohexyl 222 Benzyl do. do. do. 223 Ethylphenyl do. do. do. 224 Tridecyl do. do. do. 225 n-Tetradecyl do. do. do. 226 n-Pentadecyl do. do. do. 227 n-Hexadecyl do. do. do. 228 n-Heptadecyl do. do. do. 229 Dodecyl 4-Sulpho- H do 7 phenyl 230 Decyl do. do. do 231 do. 3 -Sulphodo. do

phenyl 232 Dodecyl do. Cl do. 233 do. do. CH do. 234 do. do. C H do. 235 do. do. C H, do. 236 do. 2'-methoxy-5'- sulphophenyl H do. 237 do. 2',6'-Di-methyl- H do.

4'-sulphophenyl 238 do. 2'-Sulpho-phenyl H do.

The forniulae of representative dyes of the foregoffg EXAMPLE 13 Examples are as follows: SOSH EXAMPLE 1 N 'CCH; SOaH CH: HO! .1 I

N N=NC-C-CH; NHC 0 0- g HO- N -C! N COOCnHzs \N/ CH3 CH3 $0.11 E?f4fP .1m--. S 03H EXAMPLE 2 N=N C C CH, 303E HOE BL N=NC-fi-CH:

110-15 N 01 N COOCmHzs HaC Cl CH 02H NH-C 0 0- 41-011,

Ha SOaH EXAMPLE 49 .F.M EE 0311 I N==N--C+-c-mn I. 1 HOH N NHCOOCuHzs \N/ HzC 11 Cl CH:

C] NH-COO V 03H CH; cm

15 16 EXAMPLE 4 R is alkyl of 6 to 18 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, cycloalkyl of 5 to 7 carbon atoms substituted by l to 3 alkyl groups of l to 6 carbon atoms or alkyl of 6 to 18 carbon atoms sub- 5 stituted by halo, hydroxy, cyano, alkoxy of 1 to 6 carbon atoms, phenyl or naphthyl, and

each of R R and R is independently hydrogen, halo, alkyl of l to 6 carbon atoms, alkoxy of l to 6 carbon atoms or alkyl of l to 6 carbon atoms suboi i stituted by halo, hydroxy, cyano, alkoxy of l to 6 carbon atoms, phenyl or naphthyl, wherein each halo is independently fluoro, chloro,

bromo or iodo. chloro, EXAMPLES OF APPLICATION 2. A compound according to claim 1 wherein R is hydrogen, halo, alkyl of 1 to 6 carbon atoms or alkyl of l to 6 carbon atoms substituted by halo,

' sogii" rio Nn-cod-o in, N

Exhaust Dyeing 100 parts of wool fabric are wet out and entered into a dyebath at 40 consisting of 4,000 parts of water, 10 h d lk f l t 6 b t parts of anhydrous sodium sulphate and 2 parts of the 3? cyano a my 0 0 car on a mm or dye of Example 1. The dyebath is raised to the boil in 20 R5 is alkyl of 6 to 18 Carbon atoms, cycloalkyl of 5 30 minutes and held at-the boil for 1 hour. 4 parts of to 7 carbon atoms cycloalkyl of 5 to 7 carbon glacial acetic acid are then added and dyeing is continatoms substituted by 1 to 3 alkyl groups of 1 to 6 for a further 30 the P' Durmg dyemg A carbon atoms or alkyl of 6 to 18 carbon atoms subthe water lost by evaporation is continuously replaced. stituted by halo, hydroxy, cyano, alkoxy of 1 to 6 On removal from the bath, the fabric is rinsed with carbon atoms or phenyl and water and dried. It is dyed a greenish yellow shade. each f R6, R7 and is independently hydrogen, Thls method sultable for dyeing synthetlc p y halo, alkyl of l to 6 carbon atoms, alkoxy of l to ide fibres with the disclosed dyes, on which they show 6 carbon atoms or alkyl f 1 to 6 carbon atoms bgood light and wet fastness. It lS also employable for i d b h l hydroxy, cyano, alkoxyof 1 to 6 dyeing polypropylene fibres modified by the introduccarbon atoms or phenyl, I tion of basic groups, the dyeings on these fibres being 3, A compound according to l i 2 of similarly good quality. gfi V I '1 n W Printing R is hydrogen, halo or alkyl of l to 6 carbon atoms,

A printing paste is prepared with:

30 parts of the dye of Example 3, R is alkyl of 6 to 18 carbon atoms, cycloalkyl of 5 538 22: zi; attt tizzzsirzlai .m to 7 carbon atoms or cycloalkyl of 5 w 7 60 Sans ofthioui ea y g atoms substituted by l to 3 alkyl groups of l to 6 60 parts ofa 20% aqueous ammonium sulphate solution and carbon atoms and wwgfiz water 40 each of R R and R is independently hydrogen,

halo, alkyl of l to 6 carbon atoms or alkoxy of l to The paste is printed on a nylon fabric by one of the 6 carbon atoms standard methods, the fabric dried and the print fixed compound accordmg to clalm 3 wherem each for 3045 minutes at 102. The fabric is then soaped at halo chloro' washed Off and dried A yellow print with good 5. A compound according to claim 3 having the forfastness properties is obtained. An equally good print mula is obtained when intermediate drying is omitted. On Ra wool and other natural polyamide fibres, prints with similar good properties are obtained by this method.

What is claimed is: NHCOOR, HO 1. A compound of the formula so n R R1 R: I

N=N- C C-CH: 5 5

HO 1L1 Ru SOaH NHCOOR:

I wherein R R is hydrogen, halo or alkyl of l to 6 carbon atoms, )Ji each of R R and R is independently hydrogen, halo, alkyl of l to 6 carbon atoms or alkoxy of l to Sosa 6 carbon atoms, and wherein R is alkyl of 6 to 18 carbon atoms, cyclohexyl or cy- R is hydrogen, halo, alkyl of l to 6 carbon atoms or clohexyl substituted by l to 3 alkyl groups of l to alkyl of l to 6 carbon atoms substituted by halo, 6 carbon atoms. hydroxy, cyano, alkoxy of 1 to 6 carbon atoms, 6. A compound according to claim 5 having the forphenyl or naphthyl, mula wherein R is hydrogen, chloro or methyl,

each of R R and R is independently hydrogen, halo, alkyl of 1 to 6 carbon atoms or alkoxy of l to 6 carbon atoms, and

R is alkyl of 6 to 18 carbon atoms, cyclohexyl or cyclohexyl substituted by 1 to 3 alkyl groups of l to 6 carbon atoms.

7. A compound according to claim 1 having the for- R is hydrogen, chloro or methyl,

each of R R and R is independently hydrogen, halo, alkyl of l to 6 carbon atoms, alkoxy of l to 6 carbon atoms or alkyl of 1 to 6 carbon atoms substituted by halo, hydroxy, cyano, alkoxy of l to 6 carbon atoms, phenyl or naphthyl, and

R is alkyl of 6 to 18 carbon atoms, cyclohexyl, cyclohexyl substituted byl to 3 alkyl groups of 1 to 6 carbon atoms or alkyl of 6 to 18 carbon atoms sub stituted by halo, hydroxy, cyano, alkoxy of l to 6 carbon atoms, phenyl or naphthyl.

8. A compound according to claim 7 having the for- R is hydrogen, chloro or methyl,

R, is hydrogen, halo or alkyl of l to 6 carbon atoms,

R, is hydrogen, halo, alkyl of l to 6 carbon atoms or alkoxy of l to 6 carbon atoms, and

R is alkyl of 6 to 18 carbon atoms, cyclohexyl, cyclohexyl substituted by l to 3 alkyl groups of l to 6 carbon atoms or alkyl of 6 to 18 carbon atoms substituted by halo, hydroxy, cyano, alkoxy of l to 6 carbon atoms, phenyl or naphthyl.

9. A compound according to claim 8 wherein R is alkyl of 6 to 18 carbon atoms, cyclohexyl or cyclohexyl substituted by l to 3 alkyl groups of l to 6 carbon atoms. 10. A compound according to claim 9 wherein R is alkyl of 6 to 18 carbon atoms, cyclohexyl, p-

ethylcyclohexyl, p-tert-butylcyclohexyl or 3,3,S-trimcthylcyclohexyl. 11. A compound according to claim 1 having the for- 10 mula soarr R3" N=NCCCH3 NHCOOR 9 III R8 S03E- wherein R is hydrogen, chloro or alkyl of l to 4carbon atoms, 2 5 each of R R and R,," is independently hydrogen,

chloro, methyl or methoxy, and R is alkyl of 7 to 17 carbon atoms, cyclohexyl, p-

ethylcyclohexyl, p-tert-butylcyclohexyl or 3,3,S-trimethylcyclohexyl. 12. A compound according to claim 11 having the formula 's'cifi 4 A 7 R3" N=NC-CCH;

NHCOOR' N R is hydrogen, chloro or alkyl or 1 to 4 carbon atoms, R,,"' is hydrogen, chloro or methyl, R is hydrogen, chloro, methyl or methoxy, and R is alkyl of 7 to 17 carbon atoms, cyclohexyl, pethylcyclohexyl, p-tert-butylcyclohexyl or 3,3,S-trimethylcyclohexyl. 13. A compound according to claim 11 having the formula =NC--C-Clh J5 NHCOOCuHzr \N/ 14. A compound according to claim 11 having the formula S=H 17. A compound according to claim 11 having the formula .N:N-C---CCII:|

. soar o c 1 HO NH 00 111 as N 5 N ..N C C-CIIJ 1roii mo 01 CH: N NHCOO AICHQ ('31! Cl 0311 l0 8 15. A compound according to claim 11 having the .031! formula H v Y "n W 18. A compound according to claim 11 having the SOEH 15 formula MM SOaI-I N NC---C-OH3 N==NCCCH1 HO N ll NHCOOCHHZS CH: HOC N NH-COO 01 H 0 c1 7 16. A cdniiaoinid ofiiHQtHElaim 11 having the 15 A corrioound according to claim 11 having the formula formula soar! V HM.,V .W r k.ri .c n SOBH -N=N-CCCH3 --N---'--=NC--(|1CHa HO- N (h HOML l mr-ooo-wmml N l NHCOO -01 o a CH; 01 or 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 wherein R3 is hydrogen, halo, alkyl of 1 to 6 carbon atoms or alkyl of 1 to 6 carbon atoms substituted by halo, hydroxy, cyano, alkoxy of 1 to 6 carbon atoms or phenyl, R5 is alkyl of 6 to 18 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, cycloalkyl of 5 to 7 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 6 carbon atoms or alkyl of 6 to 18 carbon atoms substituted by halo, hydroxy, cyano, alkoxy of 1 to 6 carbon atoms or phenyl, and each of R6, R7 and R8 is independently hydrogen, halo, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms or alkyl of 1 to 6 carbon atoms substituted by halo, hydroxy, cyano, alkoxy of 1 to 6 carbon atoms or phenyl.
 3. A compound according to claim 2 wherein R3 is hydrogen, halo or alkyl of 1 to 6 carbon atoms, R5 is alkyl of 6 to 18 carbon atoms, cycloalkyl of 5 to 7 carbon atoms or cycloalkyl of 5 to 7 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 6 carbon atoms, and each of R6, R7 and R8 is independently hydrogen, halo, alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms.
 4. A compound according to claim 3 wherein each halo is chloro.
 5. A compound according to claim 3 having the formula
 6. A compound according to claim 5 having the formula
 7. A compound according to claim 1 having the formula
 8. A compound according to claim 7 having the formula
 9. A compound according to claim 8 wherein R9 is alkyl of 6 to 18 carbon atoms, cyclohexyl or cyclohexyl substituted by 1 to 3 alkyl groups of 1 to 6 carbon atoms.
 10. A compound according to claim 9 wherein R9 is alkyl of 6 to 18 carbon atoms, cyclohexyl, p-ethylcyclohexyl, p-tert-butylcyclohexyl or 3,3,5-trimethylcyclohexyl.
 11. A compound according to claim 1 having the formula
 12. A compound according to claim 11 having the formula
 13. A compound according to claim 11 having the formula
 14. A compound according to claim 11 having the formula
 15. A compound according to claim 11 having the formula
 16. A compound according to claim 11 having the formula
 17. A compound according to claim 11 having the formula
 18. A compound according to claim 11 having the formula
 19. A compound according to claim 11 having the formula 